Conversion Of Methyl Oleate Research Articles

Transesterification of methyl oleate for sustainable production of biolubricant: Process optimization and kinetic study

Trimethylolpropane fatty acid triester (TFATE) is a promising biolubricant as an environmentally friendly substitute to conventional mineral-based lubricants. However, the issues of extensive energy consumption from vacuum maintenance and feedstock saponification caused by strong alkaline catalysts exist in current TFATE-based biolubricant synthesis. Here, sustainable production of biolubricant was achieved with methyl oleate (MO) from non-edible oil sources as the feedstock and moderate alkaline K2CO3 as the catalyst. Nitrogen gas stripping method instead of vacuum was adopted for methanol removal. The effects of agitation speed, N2 flow rate, catalyst amount, MO to trimethylolpropane (TMP) molar ratio and temperature on MO conversion and TFATE selectivity were examined. The TFATE selectivity reached 95.6% under the optimized conditions. Leaching tests indicated neglectable K2CO3 dissolution in reaction products. The kinetic parameters for the three consecutive transesterification reactions were calculated. In addition, the synthesized biolubricants exhibit low acid value and volatility, moderate iodine value, superior thermal stability, and good rheological and frictional properties.

Spongy titanosilicate promotes the catalytic performance and reusability of WO3 in oxidative cleavage of methyl oleate.

A tungsten containing catalyst catalyzed oxidative cleavage of methyl oleate (MO) by employing H2O2 as an oxidant and is known as an efficient approach for preparing high value-added chemicals, however, the tungsten leaching problem remains unresolved. In this work, a binary catalyst consisting of tungsten oxide (WO3) and spongy titanosilicate (STS) zeolite is proposed for MO oxidative cleavage. The function of STS in this catalyst is investigated. On the one hand, STS converts MO to 9,10-epoxystearate (MES), which further forms nonyl aldehyde (NA) and methyl azelaaldehydate (MAA) with the catalysis of WO3. In this way, MO oxidation and hydrolysis that generates unwanted diol product 9,10-dihydroxystearate (MDS) decreases obviously. On the other hand, STS decomposes peroxide and promotes the conversion of soluble peroxotungstate to insoluble polytungstate. Meanwhile, these tungsten species are allowed to precipitate on its surface instead of remaining in the liquid phase owing to its relative large specific area. Therefore, tungsten leaching can be reduced from 37.0% to 1.2%. Due to the cooperation of WO3 and STS, 94.4% MO conversion and oxidative cleavage product selectivity of 63.1% are achieved, and the WO3–STS binary catalyst maintains excellent catalytic performance for 8 recycling reactions.

Organic groups-regulated high-efficiency catalysis of hybrid Ti-Containing mesoporous silicates for Bi-Phase interfacial epoxidation

The sluggish interfacial mass transfer usually hinders the achievement of high-efficiency catalytic transformation of biomass, especially for solvent-free immiscible reagent systems. Herein, amphiphilic hybrid Ti-containing catalysts in situ incorporated with organic groups (Cn-Ti-HMS) were developed for boosting biphasic solvent-free epoxidation of methyl oleate (MO) with H2O2. Benefiting from the mutual effect between organic/inorganic precursors, the resulting low-defect catalysts exhibit well-mediated surface hydrophilic/hydrophobic balance and porosity by incorporating alkyl groups. Such mediation effect exhibits two superiorities: i) accelerated adsorption of reactants by amphiphilicity; ii) boosted substrate or product diffusion by porosity property. As such, remarkably promoted catalytic properties were achieved when compared with conventional Ti-HMS. Typically, methyl-functionalized C1–Ti-HMS-50 displays the optimal catalytic performance with a 95% conversion of MO. Further mechanism study recognizes the dominant role of surface wettability and Si–OH defects content in influencing MO conversion and epoxidized MO selectivity.

PLANT OIL VALORIZATION BY CROSS-METATHESIS REACTIONS: SYNTHESIS OF FINE CHEMICALS FROM METHYL OLEATE

This work studies the production of high-value compounds by the cross-metathesis of methyl oleate (MO) with ethylene, cinnamonitrile and cinnamaldehyde using the 2nd generation Hoveyda-Grubbs complex (HG) as catalyst, either dissolved in toluene or supported on silica. Reactions were carried out in batch reactors between 313 and 343 K. The yield to cross-metathesis products (YC-M) for the MO cross-metathesis with cinnamonitrile and cinnamaldehyde increased with the initial molar reactant ratio (RCN/MO, RCA/MO), reaching YC-M values of 82% and 95%, respectively, at R = 7. No catalyst deactivation took place during the 400-min catalytic runs. The liquid-phase cross-metathesis of MO with ethylene (ethenolysis) was performed over HG(10%)/SiO2 catalysts, producing 1-decene and methyl 9-decenoate, a valuable intermediate for the synthesis of pheromones. At RC2/MO = 2.5, the selectivity to ethenolysis products was 77% at 82% MO conversion. The MO self-metathesis was the only side reaction observed in all the catalytic tests.

Ethenolysis of Renewable Methyl Oleate Catalyzed by Readily Accessible Supported Group VI Oxo Catalysts

The conversion of methyl oleate by cross-metathesis with ethylene using readily accessible supported group VI oxo species was addressed. TON up to 500 and 5000 were achieved using bisgrafted tungsten- and molybdenum based systems, respectively (≡SiO)2M(═O)R2 (M = W, R = CH2SiMe3, M = Mo, R = CH2CMe3). In the case of molybdenum, these results are comparable to those obtained by Mo-based systems in homogeneous catalysis. Optimization studies showed that ethylene pressure plays a major role in these systems, with inhibition at high pressure resulting from degenerated metathesis involving ethylene and α-olefins.

Ti-sites environment-mediated hierarchical TS-1 catalyzing the solvent-free epoxidation: The remarkably promoting role of alcohol modification

The solvent-free epoxidation of vegetable oils-derived compounds is in great demand due to its green initiative and economic efficiency. Herein, we showcase a persuasive strategy for functionalizing hierarchical TS-1 (HTS-1) with alcohol to achieve remarkably enhanced catalytic activity and selectivity of methyl oleate (MO) epoxide with H2O2 as an oxidant. The effects of alcohol types, treatment temperature and time on the catalytic performance of modified HTS-1 were investigated. The functionalization of HTS-1 with ethanol was proven to be more beneficial to enhance catalytic performance than methanol and steric effect should be taken into account when using bulkier alcohol such as isopropanol. The optimal catalytic property was achieved over ethanol-functionalized HTS-1 through a facile treatment procedure (ambient temperature, 10 h). As a result, the MO conversion could reach as high as 92.7%, overwhelming that afforded by pristine HTS-1 (only 56.9%). This strategy unfolds the following multiple merits: (i) reducing non-framework Ti species and creating accessible channel for MO diffusion; (ii) increasing hydrophobicity of catalyst accompanied by the defect-mending; (iii) elevating electrophilicity of Ti active sites to obtain more electrophilic O as the active oxygen-donating species. Such merits are responsible for significantly improved catalytic activities of HTS-1.

Epoxidation of Methyl Oleate and Unsaturated Fatty Acid Methyl Esters Obtained from Vegetable Source over Ti-Containing Silica Catalysts

With different oxidants (aqueous H2O2 or cumene hydroperoxide), Ti-containing silica catalysts (hierarchical TS-1, Ti-MCM-41, and Ti-HMS) were applied as catalysts for the epoxidation of methyl oleate (MO) and vegetable-derived unsaturated fatty acid methyl esters (FAMEs). We found that the catalytic performances of titanium silicalites were highly dependent on oxidant types. For the epoxidation of MO over hierarchical TS-1 (HTS-1), aqueous H2O2 is a better oxidant compared with cumene hydroperoxide (CHP). Benefiting from good molecular accessibility and high activity of Ti sites, combined with high hydrophobicity, ultra-high-yield epoxides were obtained over HTS-1. In contrast, CHP was more favorable for Ti-HMS catalyst, which was beneficial to selective conversion of MO into epoxide under solvent-free conditions. The superior catalytic performance was ascribed to the high surface area and pore volume of Ti-HMS. Furthermore, the corresponding structure–catalytic performance relationships and reusability ...

Water-Retaining Polymers in Organic Solvent Increase Lipase Activity for Biodiesel Synthesis

Background: Biocatalyzed esterification reactions in non-aqueous media require water removal materials and optimized enzyme formulations to improve reaction rate and conversion. We have tested a lipase biocatalysis process using anionic polymeric chains of polyacrylate as super-absorbent of water in the conversion of methyl oleate from oleic acid and methanol and in toluene as reaction medium. The water removal material that we used also for the enzyme immobilization is commercially named Aquasorb 3005K2 (herein called Aquasorb). Methods and findings: The synthesis of methyl oleate was catalyzed by Candida rugosa lipase or lipase G from Penicillium camemberti in the presence or absence of Aquasorb. The simple addition of Aquasorb to the reaction media of the lipase (commercial sample) catalyzed reaction allowed an enzyme activity 20% and 40% higher than that in the absence of Aquasorb for lipase from C. rugosa and lipase G, respectively. Furthermore, for the commercial form of lipase G, when used in the presence of Aquasorb, it was obtained a higher conversion of esterification (93% instead of 60%). Aquasorb was used also as support for the adsorption of the enzyme (via hydrogel formation followed by lyophilization) producing a lipase that was 100% and 60% more active than the enzyme dissolved in buffer in the absence of Aquasorb and lyophilized. However, these lipase formulations showed only about 20 % activity compared to when dry Aquasorb was simply added to the non-aqueous reaction medium. Conclusions: The use of Aquasorb appears beneficial as additive in esterification reactions (e.g., for biodiesel production) catalyzed by lipases in non-aqueous reaction media.

MoO2 Formed on Mesoporous Graphene Oxide: Efficient and Stable Catalyst for Epoxidation of Olefins

A novel mesoporous MoO2 composite supported on graphene oxide (m-MoO2/GO) has been designed and applied as an efficient epoxidation catalyst. The m-MoO2/GO composite was characterised by X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, Brunauer–Emmet–Teller surface area analysis, field emission scanning electron microscopy, and transmission electron microscopy. Compared with pure mesoporous MoO2 (m-MoO2) and amorphous MoO2-graphene oxide (a-MoO2/GO), m-MoO2/GO exhibits the best catalytic activity. The conversion and selectivity for cyclooctene are both over 99 % in 6 h. Remarkably, the mesoporous structure in m-MoO2/GO which derives from SiO2 nanospheres endows the catalyst better catalytic performance for long chain olefins: the conversion of methyl oleate can be as high as 82 %. Such a robust catalyst can be easily recycled and reused five times without significant loss of catalytic activity. This novel catalyst is promising in the synthesis of epoxides with a long carbon chain or large ring size.

Cross metathesis of methyl oleate (MO) with terminal, internal olefins by ruthenium catalysts: factors affecting the efficient MO conversion and the selectivity

Cross metathesis (CM) of methyl oleate (MO) with cis-4-octene, cis-stilbene, allyltrimethylsilane by RuCl2(PCy3)(IMesH2)(CHPh) yielded CM products with high MO conversion, high selectivity; the effect of olefin substituents, conditions was explored.

Modelling and optimization of Candida rugosa nanobioconjugates catalysed synthesis of methyl oleate by response surface methodology

Esters, such as methyl oleate, are functionally important compounds in many industrial sectors, mainly as components for manufacturing of emulsifiers, detergents, intermediate stabilizers and wetting agents. Acid functionalization of multi-walled carbon nanotubes (F-MWCNTs) by using a mixture of HNO3 and H2SO4 (1:3, v:v) was employed as the matrix for the adsorption of Candida rugosa lipase (CRL) as nanobioconjugates (CRL-MWCNTs) for the production of methyl oleate. Structural information of the developed CRL-MWCNTs was confirmed using Fourier Transform Infrared spectroscopy, thermogravimetric analysis and transmission electron microscopy, which revealed a successful attachment of CRL onto the F-MWCNTs. Process parameters (reaction time, temperature and alcohol:acid molar ratio) were optimized for high percent conversion of methyl oleate. Structural analysis established that CRL was successfully attached to the surface of the F-MWCNTs. Under the optimized conditions, which were 13.87 h, 51 °C, molar ratio oleic acid:methanol (1:3.80), a high ester yield of 90.90% was attained. Also, under conditions of the shortest reaction time of 6 h, 47.07 °C and acid:methanol ratio of 1:2.54, the CRL-MWCNTs catalysed a 74.51% ester yield. Hence, we established that response surface methodology (RSM) can be a practical technique for the prediction of the conditions that favour the high yield production of methyl oleate. Under optimized conditions, the CRL-MWCNTs nanobioconjugates are potentially good and economical biocatalysts for the production of methyl oleate, as well as other types of commercially important fatty-acid methyl esters.

Increased functionality of methyl oleate using alkene metathesis

A series of alkene cross-metathesis reactions were performed using a homogeneous ruthenium-based catalyst. Using this technology, a variety of functional groups can be incorporated into the bio-based starting material, methyl oleate. Trans-stilbene, styrene, methyl cinnamate and hexen-3-ol have all been shown to give desirable products. Using this technology, aromatics, alcohols or additional esters can be incorporated into the products. For example, the cross-metathesis reaction of methyl oleate with methyl cinnamate by the second-generation Grubbs catalyst showed 70% conversion of methyl oleate into products where half of the observed products contain an aromatic group and over one-third of the products contain an α,β-unsaturated methyl ester. This promising green route is versatile, and with an appropriate selection of starting materials, it is applicable to the synthesis of polymer precursors, industrial fluids or any other application where the upgrade of natural oils is necessary.

Self-metathesis of methyl oleate on silica-supported Hoveyda–Grubbs catalysts

The self-metathesis of methyl oleate (MO) to yield 9-octadecene and 9-octadecene-1,18-dioate (9-OD) was studied in liquid-phase on silica-supported Hoveyda–Grubbs complex catalysts (HG/SiO2) containing 0.43–6.0wt.% HG. The reaction was carried out in a batch reactor at 303–343K and 101.3kPa, using cyclohexane as solvent. HG/SiO2 catalysts were active and highly selective for the MO metathesis reaction; equilibrium values of MO conversion and 9-OD yield were reached in 80min. No catalyst leaching took place in cyclohexane. Catalysts containing HG >0.87wt.% showed no significant deactivation after two consecutive catalytic tests.

Synthesis of Nickel Phosphide Nanorods as Catalyst for the Hydrotreating of Methyl Oleate

Arrays of nickel phosphide nanorods were successfully synthesized by nanocasting using mesostructured silica SBA-15 as a hard template (HT-Ni2P). After temperature-programmed reduction of the phosphate precursor infiltrated within the pore walls of SBA-15, the unsupported material was obtained by removing the silica matrix with diluted HF. The pore channel of the SBA-15 template stabilizes the Ni2P particles, preventing sintering after the high reduction temperature and shaping their elongated morphology. Moreover, HT-Ni2P catalyst shows an improvement in the textural properties with a significantly higher surface area than the reference sample synthesized in the absence of template. X-ray diffraction revealed that the only crystalline phase present in this material was Ni2P. On the other hand, transmission electron microscopy shows that the catalyst is mainly constituted by agglomerates of nanorods. Through EDX microanalysis the efficient removal of silicon was confirmed. Under hydrotreating conditions, nanorods of Ni2P show a fourfold enhancement in the conversion of methyl oleate with respect to conventional Ni2P synthesized in absence of hard template. Nevertheless, when these data are normalized to surface area, the specific activity of HT-Ni2P nanorods is significantly lower than that of the conventionally prepared sample. Differences in selectivity were also observed as Ni2P nanorods favored the decarboxylation reaction leading to a higher yield of n-heptadecane.

Post-synthesis of TiO2/MCM-41 from aqueous TiCl4 solution: Structure characteristics and epoxy catalytic activity

Titanium-containing mesoporous silica TiO2/MCM-41 (C) was prepared by impregnating MCM-41, pretreated by refrigeration at 278K, with aqueous TiCl4 solution as titanium precursor. In addition, TiO2/MCM-41 (H) was produced by same method but the support MCM-41 without refrigeration in order to investigate the influence of unrefrigerated pretreatment on the structure of TiO2/MCM-41. The dispersion and nature of titanium species were characterized by inductively coupled plasma mass spectrometry (ICP-MS), powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), UV–visible diffuse reflectance spectra (UV-vis DRS), standard Brunauer–Emmnett–Teller (BET), X-ray photoelectron spectra (XPS), scanning electron micrographs (SEM), transmission electron microscopy (TEM). The results indicate that TiO2/MCM-41 (C) showed better mesoscopic order, higher dispersion of titanium oxide species, stronger interaction with the MCM-41 support. But the pore size decreases from 3.4 to 2.4nm when the titanium content increases to 76.6mg/g. TiO2/MCM-41 (C2) exhibits more excellent catalytic performance than others, and the 97.6% conversion of methyl oleate (MO) and 93.1% selectivity to epoxidation methyl oleate (EMO) can be obtained at 353K for 10h.

Optimized reaction conditions for the cross-metathesis of methyl oleate and oleylamine with ethyl acrylate

The cross-metathesis of methyl oleate and oleylamine with ethyl acrylate has been studied using three different ruthenium-based second-generation catalysts. Emphasis was on determining the smallest amount of catalyst necessary for full conversion of technical grade educts. Conversion of methyl oleate is best performed in the presence of 10 equiv. ethyl acrylate without use of additional solvent whereas oleylamine cannot be used directly and protection of the amino group is necessary. An easy protection procedure for oleylamine with acetic anhydride was developed and the best results for cross-metathesis of N-acetyloleylamine were obtained in toluene solution. .

Solvent-free selective epoxidation of fatty esters over a tungsten-based catalyst

A solvent-free, rather complete and selective cis epoxidation of methyl oleate (MO) using a tungsten-containing catalyst called “Tetrakis”. High epoxide yields have been obtained by adjusting the reaction parameters (reaction time, temperature, gas phase, oxidant molar ratio and concentration). The highest selectivities are the result of a synergetic effect of hydrogen peroxide and air (or oxygen) used as oxidizing agents that decreases the MO dimerization and then favour the complete conversion of MO into its epoxide.

Synthesis of alkenyl succinic anhydrides from methyl esters of high oleic sunflower oil

Alkenyl succinic anhydrides (ASA) have been prepared by ene‐reaction of high‐oleic sunflower oil methyl esters with maleic anhydride in a 50% xylene medium. Response surface methodology (RSM) was used to investigate the influence of two factors: reaction temperature and molar ratio between maleic anhydride (MA) and methyl esters (SME). The studied parameters in 8‐h reactions were the methyl oleate conversion, the distillation yield in ASA, and responses allowing the indirect estimation of side reaction products: clarity index and dynamic viscosity. The highest yield in ASA (>70%; clarity index ≈10) was reached for a temperature of 240–250 °C with a molar ratio of 1.5–1.7. But for an industrial application requiring minimized side products (clarity index >40), the optimal synthesis conditions were: temperature between 220 and 235 °C and molar ratio of 1.2–1.35 (yield ≈55%). Such conditions did not provide a medium free of side products, even if xylene decreased their formation. Compared to solvent‐free synthesis, conversion was lower with xylene. With solvent, higher temperatures were needed to reach the same yields. Supplementary heating compensated the reagent dissolution effect that slows down the kinetics of the ene‐reaction. The influence of reaction time at 220 °C with a MA/SME ratio of 1.2 in a 50% xylene medium was studied. A reaction time of 8–10 h provided a good compromise between ASA yield and side products.

Étude paramétrique du craquage catalytique de l’oléate de méthyle

Parametric study of methyl oleate catalytic cracking. The limitation of oil resources leads to the development of new technologies that can exploit more fully renewable energies such as fatty matter (rapeseed or sunflower oils) and their derivatives. The general aim of this study is to produce chemical base products with high added value in lubricant and detergent sectors. The purpose of this research was to investigate the conversion of methyl oleate, a major derivative from rapeseed oil, to hydrocarbons. In support of our knowledge in vegetable oil derivatives cracking, a laboratory pilot was conceived in Nancy. To describe the running conditions of the fixed bed reactor, the physical quantities (profile of temperature, time of contact...) were defined. Liquid and gaseous products were analysed by gas phase chromatography and CO–CO 2 by infrared spectrometry. The conversion of methyl oleate, selectivities and yields of cuts of products showed that there is a narrow link between the nature of the catalyst and product distribution; the best conversion of methyl oleate was obtained with activated alumina. This emergent lipochemistry could lead to new processes and to new products (lubricants, surfactants) coming from derivatives issued from vegetable oils and therefore capable of keeping the biodegradability of the raw matter. To cite this article: F. Billaud et al., C. R. Chimie 7 (2004) .

Production of alkenyl succinic anhydrides from low‐erucic and low‐linolenic rapeseed oil methyl esters

AbstractFatty acid methyl esters from low‐erucic and low‐linolenic rapeseed oil were used to produce alkenyl succinic anhydrides. A second‐order Doehlert uniform network design was used to investigate the influence of the reaction temperature and the molar ratio between the maleic anhydride and the main unsaturated rapeseed oil methyl esters on the yield of alkenyl succinic anhydride from methyl oleate. Further subjects of investigation were the conversion of methyl oleate, the formation of side reaction products, the Gardner color of the product and its viscosity, and finally the content of maleic anhydride remaining in the medium after the reaction. Alkenyl succinic anhydride from methyl oleate was isolated by column chromatography and analyzed by IR, 1H‐ and 13C‐NMR and MS. The optimal reaction conditions for obtaining the maximum yield of alkenyl succinic anhydride from methyl oleate in the experimental domain (80%) were 210‐220 °C and a maleic anhydride/rapeseed oil methyl ester molar ratio of 1.5. However, the products synthesized in these conditions showed a high degree of viscosity (0.45 kg m−1 s−1), a very dark color (18 Gardner color) and a high content of undesirable side products (6%), which could hinder their industrial use. A molar ratio of less than 1.5 led to a clearer and less viscous product, although with a lower alkenyl succinic anhydride content.